Polymers of acrylyltriazine-aliphatic amine reaction products



groups present.

Patented Oct. 28, 1952 UNITED STATES PATENT OFFICE POLYMERS OF ACRYLYLTRIAZINE-ALI- PHATIC AMINE REACTION PRODUCTS Ernst Zerner and Marcel Gradsten, New York,

N. Y., and Fred W. West, Peace Dale, It. I., assignors to. Sun Chemical Corporation, New York, N. Y., a corporation of Delaware No Drawing. Original application June 10, 1948, Serial No. 32,264. Divided and this application September 2-2, 1950, Serial No. 186,316

GClaims. (o1. 280-88.3)

H C. CH2

o H: whereRrepresents substituted or unsubstituted open. chainhydrocarbon radicals. One of the materials described in the above identified copending application is hexahydro-1,3,5-triacrylyl-s-triazine- Also there is described in this copending application hexahydro-1,3,5trimethacrylyl-s-triazine.

We have found according to. the present invention that certain new and useful products may be obtained by proper further reactions with acrylyl-s-triazine.

The above derivatives of triazines contain in their molecular structure three vinylidene groupings. In accordance with the present invention derivatives are secured by reactions which lead bythe formation of addition compounds to saturation of one, two or three of the vinylidene Such products may be described by the formula N\'} 1150 CH2 II R';ON N }Ri 0 H2 where R3 is a radical which is selected from the group consisting of CA=CHA where A is selected. from -the group. consisting; of hydrogen;

halogen. and..lower alkyl radicals and. addition products of CA=CHA and where R4 is anad- 2 dition product of CA=CHA, as described and claimed in a copending application. filed on June 10, 1948, Serial No. 32,263, application of Ernst Zerner and Mark W. Pollock.

Of these materials those which contain one or two vinylidene groups present in the molecule of the products may be further treated to eifect polymerization of this material, either alone or admixed with another polymerizable monomer to furnish valuable resinous materials which may be employed in various arts in which such materials find application, for instance as coating materials for paper, wood, metal and cloth, and in conjunction with drying oils in coatings.

The polymerized materials of the present invention may be described as polymerization products of compounds of the general formula where R1 represents the radical CA=CH2, where A is selected from the group consisting of hydrogen, halogen and lower alkyl radicals and where R2 is a radicalselected from the group consisting of CA=CH2 and addition products of CA=CH2.-

As described in the above identified copending. application Serial No.. 16,135, hexahydro-l,3,5-- triacrylyl-s-triazine satisfactorily may be prepared as follows: In a suitable reaction vessel provided with a stirrer, reflux condenser, thermometer and a dropping funnel are placed 265 parts by weight of acrylonitrile dissolved in 400 parts by weight of benzene, together with 2.8 parts of concentrated sulfuric acid. In the dropping funnel is placed a solution of parts by weight of trioxane dissolved in 400 parts by weight of benzene. The acrylonitrile solution is warmed, satisfactorily'on a boiling water bath, and the material in the dropping funnel added at a rate such that the mixture is maintained under reflux condition. When all of the solution in the dropping funnel has been added, the resulting admixture is heated under reflux conditions for an additionalperiod of approximately three hours.

Subsequently the mixture; which; contains; a yellow precipitate; is allowed. to: stand? overnight and the precipitate then separated by filtration and subsequently recrystallized from ethanol.

As described in the above identified copending application, Serial No. 16,135, similar products may be obtained using as starting materials nitriles such as methacrylonitrile, alpha chloracrylonitrile and similar nitriles containing a vinylidene group.

Triazines of the above type and containing three vinylidene groups may bev represented by the formula e 26 1 CH2 g (imam-one N lGA=C-Hi where A is hydrogen, halogen or a lower alkyl radical. Such materials, in accordance with the present invention, may be subjected to polymerization reactions either alone or admixed with other polymerizable monomers to form valuable resinous reaction products.

Illustrative of the preparation of such polymer materials are the following examples.

Example I A solution containing 6 per cent of hexahydro- 1,3,5-triacrylyl-s-triazine in 20 per cent acetic acid is heated to boiling. Upon such heat treatment a polymer material is precipitated from solution and may be separated therefrom for further utilization.

In the above preparation the rate of formation of the polymer material can be increased by utilization of a peroxide in the reaction solution.

Example If A per cent solution of hexahydro-1,3,5-triacrylyl-s-triazine in chloroform together with 0.1 per cent of benzoyl peroxide, based on the triazine, is warmed to effect evaporation of the chloroform and subsequently heated for a period of approximately one-half hour at a temperature of 130 C. in a suitable container. A brittle white. insoluble polymer material is secured.

Polymerization of such materials may also be effected, for example, in the presence of a textile material in which case a product is obtained which comprises the textile material impregnated with the resinous products of the present invention.

Also, according to the present invention as above set forth, copolymerization may be effected, as illustratively set forth in the following example.

Eram-ple III A mixture containing 99.65 per cent by weight of styrene, 0.25 per cent by weight of hexahydro- 1,3,5-triacrylyl-s-triazine and 0.1 per cent of benzoyl peroxide is heated to 60 C. to effect formation of a polymer material. The rate of polymerization is much more rapid with the triazine present than in its absence, and the product obtained is a cross linked polymer, as distinguished from linear polymers which are obtained by the polymerization of styrene. Evidence for this is the fact that the copolymerization product is insoluble in xylol, whereas polymers of styrene are soluble in such solvent. 7

Another aspect is the preparation of addition products of triazines of the type described above in which one, two or three of the vinylidene groups present are converted into saturated groupings by suitable reaction. A variety of different materials can be employed to react with the vinylidene groups present in the triazines to add thereto and to form saturated vinylidene groupings. Illustrative of some of the materials which will react are compounds such as sodium bisulfite, alcohols, halogens, conjugated diolefins, amines, compounds having an active hydrogen, hydrogen sulfide, and mercaptans.

In this addition reactions involving the particular triazines hereinbefore described, which contain three vinylidene groups in the molecule, and the above illustrative additive compounds, except as hereinafter set forth, saturation of the vinylidene groups is effected by the addition of a hydrogen atom of the additive compound a to the carbon atom of the vinylidene group which is adjacent to the carbonyl group of the triazine compound, the remainder of the molecule of the additive compound becoming attached to the terminal carbon atoms of the said vinylidene group. Additive compounds such as the halogens efiect saturation by adding each of the atoms of the halogen molecule to each of the carbon atoms of the vinylidene group, while such additive compounds as butadiene apparently form cyclic addition products with the two carbon atoms of the vinylidene group.

Where the above illustrative materials are employed to efiect reaction with triazines containing vinylidene groups, either one, two or three of the vinylidene groups may be saturated, depending upon the amount of reacting materials utilized. Where only one or two of the vinylidene groups is thus saturated, the resulting material may be polymerized, either alone or in conjunction with other polymerizable monomers to form a resinous product, whose characteristics will be dependent in part upon the modifying reacting material employed to effect saturation of the vinylidene groupings prior to polymerization.

Illustrative examples setting forth this aspect include the following.

Example IV 20 parts by weight of hexahydrol,3,5-triacrylyl -striazine is dissolved in 500 parts of water at approximately 75 C. When solution is completed there is added thereto 8.2 parts by weight of sodium bisulfite which corresponds to one molecular equivalent of sodium bisulfite per mol of triazine. Addition of the bisulfite is effected while maintaining the solution under agitation conditions. When addition of the bisulfite is completed, the admixture is cooled and may be filtered to remove traces of impurities. A slightly milky solution results. Upon drying of this solution under vacuum conditions, there is obtained a clear White solid which is easily soluble in water and which does not melt or decompose at temperatures up to 250 C.

Example V Aqueous solutions of the product of Example IV, upon treatment with 30 per cent hydrogen peroxide solution polymerized to give a resinous product. i

5. Example VI A -6 per cent solution of the product of Example IV in water, together with two drops of 30 per cent hydrogen peroxide per 100 parts by weight of solution was heated at boiling for ten minutes. The resulting solution was cooled and was employed in normal padding operation to efiect impregnation of percale. After padding was completed, the impregnated percale was dried at 100 C. The treated material was remarkably stiiIer than the original untreated goods, such effect being caused by the polymerization of the sodium bisulfite addition productof hexahydro-1,3,5-triacrylyl-s-triazine in situ in the fabric material.

Example VII 20 parts by weight of hexahydro-l,3,5-triacrylyl-s-triazine is dissolved in 500 parts by weight of water at 75 C. When solution is completed there is added, with agitation, 16.4 parts by weight of sodium bisulfite corresponding to two molecular equivalents of'sodium bisulfite per mol of triazine. After addition of the bisulfite is completed, the admixture is cooled and filtered to remove impurities. Upon drying of the filtrate under vacuum condition, a clear white watersoluble product is secured which does not melt at temperatures up to 250 C.

Example VIII Polymerization of the product of Example VII is obtained by dissolving theproduct in water and treating the aqueous solutionwith 30 per cent hydrogen peroxide.

Example IX increase in weight tofr'the: reaction admixture at intervals:

groupssare'isaturated; a product .isobtained which may: be." polymerized; Polymerization satisface torily-is effected. inthe presence of aperoxide polymerization: catalyst.

Eaampld'Xl reacted with conjugated diolefins such as butadiene in which case the reaction which occurs appears'todnvolve the formation of :a cyclic compoundz'by 'a .1,4 addition. of: the; vinyl-idenecgroup: 1

toi'theconjugated diolefin. wliererlessv thanall of the :vinyli'd'ene: groups present: are; saturated;.

a product is: obtained which maybe polymerized.

One satisfactory methodzof efiectin'g isuch reace tion is illustrated in a prior granted patent which.

shows the reaction .betweenacrylonitrile and con- Hexahydro-l,3,5-triacry1yl-s-triazine is treated as. described in Example V'II exceptthat there is used 24.6 parts by weight of sodium bisulfite. corresponding to three molecular equivalents of;

A water sodium bisulfite per mol of 'triazine. soluble product is secured which does not undergo polymerization.

Example X completion of this addition the admixture stirred fora length of time sufilcient to complete the reaction which with the quantities above described is approximately, Shours. At the end of this reaction period the mixture is made acidic by addition of glacial acetic acid thereto. The reaction admixture is then diluted with 1 times itsvolume of ether and filtered. The filtrate is evaporated to remove ether and chloroform and the" residue washed with water and then dissolved in ether. The ether. solution is dried satisfactorily with sodium sulfate and then filtered. .To. remove ether the admixture is distilled: under. reduced. pressure. A brown viscous oil, the butyl' alcohola'ddition product of hexahydro-l,3,5-triacrylyl-s-triazine is obtained.

The product, uponheatingtogether with benzoyl peroxide, forms a resinous product.

Hexahydro-l,3,5-triacrylyl-s-triazine may be chlorinated by bubbling chlorine into the material in the presence of a small amount of a polymerization inhibitor such as hydroquinone in an jugated diolefins, nam'ely'U. S. P. No. 2,217,632, dated "OctoberB; .1940.

. Example XII ln a suitable reaction vessel wereplacedi 50 parts of chloroform-and 12:5 parts'by-weightaof.

hexahydro-1,3,5-triacrylyl-s triazine. The mixmately 37 C. After addition of the amine'ris completed. the. reaction admixture isstirred.. for a period. of timesufficient to insure completion of the .reactionwhich with the. quantities above describedv is approximately 1.25 hours. Themixture then may be: allowed-to stand-for several' hours and subsequently is filtered and the chloroform. removedtheref-rom. by distillation under reducedipr'essure. A. clear. viscous liquidlm'aterial is obtained.

Example XIII.

Example XI V Following the procedure described in Example XII and utilizing 16 parts by weight of decyl amine there is. secured an addition' product in which two/of the three vinylidene groups of the triazines" have been saturated. This product polymerizes at a rate slower than the product of Example XIII and serves satisfactorily as a plas-- ticizingpolymer tobe used in conjunction with the polymer of Example. XIII.

Example XV In. a reaction vessel areplaced 50 parts of' nchloroform and 12.5 parts by weight-of hexa-' Where chlorination'iszdiscontinuedat" a point: where less than: all of the; vinylidene hours, stirring then discontinued and the mixture allowed to stand for several hours. It, then is filtered and the filtrate evaporated under reduced pressure to remove the chloroform. A white Example XVI The procedure described in Example XV is followed except that there is used 8 parts by weight of diethyl amineto give a product which is an addition product containing two molecular equivalents of diethyl amine per mol of triazine. The product is water-soluble and is a. surface active material.

Example XVII The procedure described in Example XV is followed except that there is utilized 12 parts by weight of diethyl amine to give a reaction product containing three molecular equivalents of diethyl amine per mol of triazine.

Products in which the triazines of the present invention are reacted with materials containing an active hydrogen such as fluorene may be prepared by the utilization of alkaline condensing agents. Illustrations of such reactions involving nitrile materials are set forth in U. S. P. No. 2,280,058 of April 21, 1942.

Illustrations of reaction conditions which may be employed to effect saturation of the vinylidene groups of triazines of the present invention with materials such as hydrogen sulfide are set forth in U. S. -P. No. 2,163,176 dated June 20, 1939.

,While the above described products constitute preferred embodiments of the invention, changes may be made therein without departing from the scope of the invention, as defined in the appended claims.

What is claimed is: p

1. As a new product, a polymer of a compound of the general formula where A is a member of the group consisting of hydrogen, halogen and a lower alkyl radical, where R is a member of the group consisting of hydrogen and an alkyl radical, and where R1 represents an alkyl radical.

2. As a new product, a polymer of a compound of the formula CH; tn

3. As a new product, a polymer of a compound of the formula CH; is i 11 0 CHa Hi? I l i Ge CHFC-G-N N-GCH2-OH2N C CzHs 4. As a new product, a polymer of a compound of the formula 0 o H H H I NCC--CHwN(CH2)n-CH:

CH3 z 5. As a new product, a polymer of a compound of the formula 6. As a new-product, a polymer of a compound of the formula ERNST ZERNER.

MARCEL GRADSTEN. FRED WEST.

No references cited. 

1. AS A NEW PRODUCT, A POLYMER OF A COMPOUND OF THE GENERAL FORMULA 